CN111693494B - THz wave sensor based on CNTs super surface, preparation method and application thereof - Google Patents
THz wave sensor based on CNTs super surface, preparation method and application thereof Download PDFInfo
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- CN111693494B CN111693494B CN202010436778.2A CN202010436778A CN111693494B CN 111693494 B CN111693494 B CN 111693494B CN 202010436778 A CN202010436778 A CN 202010436778A CN 111693494 B CN111693494 B CN 111693494B
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Abstract
The invention discloses a THz wave sensor based on a CNTs super surface, which comprises a substrate, wherein a thin film layer is covered on the substrate, a rectangular hole array structure is etched on the thin film layer, and a packaging layer is covered on the thin film layer. The structure of the two-dimensional periodic symmetric rectangular hole array is simple, and the processing is convenient; the process is simple and easy to realize; the method is used for detecting the pesticide residue, is simple, has high detection precision, good reliability and stability, and the minimum sensitivity is 2.0x10 ‑3 Error was 0.13%.
Description
Technical Field
The invention belongs to the technical field of detectors, relates to a THz wave sensor based on a CNTs super surface, a preparation method of the sensor and application of the sensor.
Background
Currently, the excessive use of pesticides causes an increasing problem of pesticide residues in agricultural products. Pesticide residues in agricultural products have been a threat to human health and biodiversity. Scientific researches show that long-term accumulation and retention of residual pesticides in fruits and vegetables in human bodies can cause chronic poisoning, and potential threat is brought to human health, so that a plurality of chronic diseases are induced.
The current common pesticide detection methods include immunoassay technology, instrument analysis technology and spectrum analysis technology. The immunoassay technology comprises an enzyme immunoassay technology, a radioimmunoassay technology and a gold immunoassay technology, has high specificity and high reaction sensitivity, but has the defects of large investment of early-stage equipment, high cost, possibility of false positive in detection, limited application range and the like. The instrument analysis technology comprises gas chromatography, high performance liquid chromatography, gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry, has strong analysis capability, wide detection range, stable and reliable detection result, high sensitivity and good reproducibility, has developed and matured and forms a certain industry standard, but has the defects of expensive equipment, complicated pretreatment steps and detection processes, long analysis time, insignificant specificity, and the detection can be completed only by the assistance of professional operators, thereby being unfavorable for realizing the rapid field detection of pesticide residues. Spectroscopic analysis techniques include hyperspectral imaging, infrared spectroscopy, fluorescence spectroscopy, and the like. The hyperspectral imaging and infrared spectrometry are only suitable for detecting pesticides with higher concentration, and the detection effect on trace pesticide residues is poor; because some pesticides do not have fluorescence characteristics, the application range of fluorescence spectroscopy is also limited to a certain extent.
Disclosure of Invention
The invention aims to provide a THz wave sensor based on a CNTs super surface, which solves the problem of low detection precision in the prior art.
The technical scheme adopted by the invention is that the THz wave sensor based on the CNTs super surface comprises a substrate, wherein a thin film layer is covered on the substrate, a rectangular hole array structure is etched on the thin film layer, and a packaging layer is covered on the thin film layer.
The invention further aims to provide a preparation method of the THz wave sensor based on the CNTs super surface.
The invention adopts another technical scheme that the preparation method of the THz wave sensor based on the CNTs super surface comprises the following steps:
step 5, performing surface leveling modification on the film layer, and pressing a packaging layer;
step 6, cutting windows on the packaging layer;
and 7, etching a rectangular hole array structure on the film layer to obtain the THz wave sensor.
The invention is also characterized in that:
in the film drawing process in the step 2, the drawing speed is 8-10 m/min.
The film layer comprises 40-100 layers of CNTs film which are arranged in a super-ordered way.
The length of the rectangular hole array structure is 80-150 mu m, the width is 15-35 mu m, and the period is 200-300 mu m.
A third object of the present invention is to provide a use of a THz wave sensor based on CNTs super surface.
The third technical scheme adopted by the invention is the application of the THz wave sensor based on the CNTs super surface, which is used for detecting the residual pesticide.
The detection concentration range of the THz wave sensor is 1-80 ppm.
The beneficial effects of the invention are as follows:
the THz wave sensor based on the CNTs super surface has a two-dimensional periodic symmetric rectangular hole array structure, and is simple in structure and convenient to process; the preparation method of the THz wave sensor based on the CNTs super surface has simple process and easy realization; the THz wave sensor based on the CNTs super surface has the advantages of simple detection method, high detection precision, good reliability and stability, and minimum sensitivity of 2.0 multiplied by 10, and is used for detecting pesticide residue -3 Error was 0.13%.
Drawings
FIG. 1 is a schematic structural diagram of a THz wave sensor based on CNTs supersurface in accordance with the present invention;
FIG. 2 is a side view of a THz wave sensor based on CNTs subsurface of the present invention;
FIG. 3 is a flow chart of a method for preparing a THz wave sensor based on a CNTs supersurface of the invention;
FIG. 4 shows Fano resonance fitting results and experimental results of the application of the THz wave sensor based on the CNTs super surface;
FIG. 5 is a graph of the detection results of the application of the THz wave sensor based on the CNTs super surface.
In the figure, 1, a substrate, 2, a film layer, 3, a rectangular hole array structure and 4, a packaging layer.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
A THz wave sensor based on CNTs (carbon nanotubes) super surface, as shown in figures 1 and 2, comprises a substrate 1, wherein a thin film layer 2 is covered on the substrate 1, a rectangular hole array structure 3 is etched on the thin film layer 2, and a packaging layer 4 is covered on the thin film layer 2.
A preparation method of a THz wave sensor based on a CNTs super surface comprises the following steps:
step 5, performing surface leveling modification on the film layer 2, and pressing the packaging layer 4;
step 6, cutting a window on the packaging layer 4 by utilizing a laser etching technology, wherein the area of the window is 0.6-0.8 cm 2 The laser power is 15-25W;
step 7, etching a two-dimensional periodic symmetric rectangular hole array structure 3 on the film layer 2 to provide a resonance mode for the CNTs super surface; the CNTs super surface with the two-dimensional periodic symmetric rectangular hole array structure 3 generates surface plasmons at the surface under the irradiation of incident electromagnetic waves, and the CNTs super surface appears as enhanced formants on a transmission spectrum; different detection objects are placed in the rectangular holes, so that the resonance peak characteristics can be changed; the length of the rectangular hole array structure 3 is 80-150 mu m, the width is 15-35 mu m, and the period is 200-300 mu m.
According to the invention, the THz time domain spectrum system is adopted to characterize and test the performance of the THz wave sensor, as shown in fig. 3, two enhancement formants are observed in the transmission spectrum of the terahertz wave sensor and are respectively positioned at 0.87THz and 1.62THz, and coincide with the formant positions of the first-order mode and the second-order mode of Fano resonance, which are caused by the surface plasmon resonance of the THz wave sensor, and the transmission formant mechanism is well explained by combining the SPPs dispersion relation and the Fano model.
The application of the THz wave sensor prepared by adopting the preparation method of the THz wave sensor based on the CNTs super surface is used for detecting the residual pesticide.
The THz wave sensor is utilized to detect pesticide solutions with different concentration gradients, the terahertz time-domain spectrum experimental system used for testing is in a transmission mode, and the concentration range of the detected pesticide solution is 1-80 ppm.
As shown in FIG. 4, the transmission peak of the agricultural chemical solution is a linear function of its concentration, and when the concentration of the agricultural chemical solution increases from 1ppm to 10ppm, the amplitude of the transmission formant slightly increases, the normalized amplitude variation amplitude thereof is 20%, the regression coefficient is 0.9036, and the sensitivity is 1.38X10 -2 /ppm; when the concentration is increased from 10ppm to 80ppm, the amplitude of the transmission resonance peak is sharply reduced, the normalized amplitude variation amplitude is 25%, the regression coefficient is 0.9012, and the sensitivity of the sensor is 3.0X10 -3 /ppm。
The principle of pesticide detection by the THz wave sensor is as follows: when electromagnetic waves are incident on the surface of the THz wave sensor, surface plasmons are generated at the interface of the unit structure, THz waves incident with specific polarization can be coupled to the carbon nano tube microstructure, a transmission enhancement phenomenon occurs, and an enhancement resonance peak occurs in a transmission spectrum. This enhanced formant is very sensitive to the dielectric environment at the surface of the THz wave sensor, which in turn appears to be highly sensitive to changes in pesticide concentration. With the increase of the concentration of the pesticide solution, the transmission amplitude value shows regular change, so that the pesticide solutions with different concentration gradients are detected.
When the concentration of the pesticide solution is increased from 1ppm to 10ppm, the CNTs film and the pesticide solution form an equivalent anti-reflection film, resulting in a slight increase in the amplitude of the transmission formants when THz waves are incident.
When the concentration is increased from 10ppm to 80ppm, the amplitude of the transmission formant is drastically decreased in this concentration range due to the large absorption of terahertz waves caused by the increase in the effective thickness of the film.
The THz wave sensor is highly sensitive to the change of pesticide concentration, essentially because the refractive index of the film is closely related to the dielectric constant, when the sensor is used for detecting, the refractive indexes of pesticide solutions with different concentrations are different, so that the dielectric environment around the super-surface structure is changed, and the response of the integral structure to incident THz waves is influenced.
Through the mode, the THz wave sensor based on the CNTs super surface has a two-dimensional periodic symmetric rectangular hole array structure, and is simple in structure and convenient to process; the preparation method of the THz wave sensor based on the CNTs super surface has simple process and easy realization; the THz wave sensor based on the CNTs super surface has the advantages of simple detection method, high detection precision, good reliability and stability, and minimum sensitivity of 2.0 multiplied by 10, and is used for detecting pesticide residue -3 Error was 0.13%.
Claims (3)
1. The preparation method of the THz wave sensor based on the CNTs super surface is characterized by comprising the following steps of:
step 1, vertically growing a CNTs array on a substrate (1);
step 2, pulling out the CNTs film which is arranged in a super-orderly manner on the CNTs array;
step 3, transferring the CNTs film to a substrate (1);
step 4, repeating the step 2-3, and superposing a plurality of CNTs films to obtain a film layer (2);
step 5, performing surface leveling modification on the film layer (2) and pressing the packaging layer (4);
step 6, cutting windows on the packaging layer (4);
step 7, etching a rectangular hole array structure (3) on the film layer (2) to obtain a THz wave sensor; in the film drawing process in the step 2, the drawing speed is 8-10 m/min; the film layer (2) comprises 40-100 layers of CNTs films which are arranged in an ultra-ordered manner; the length of the rectangular hole array structure (3) is 80-150 mu m, the width is 15-35 mu m, and the period is 200-300 mu m.
2. Use of the THz wave sensor prepared by the preparation method of claim 1 for detecting residual pesticide.
3. The use of the THz wave sensor prepared by the preparation method of the THz wave sensor based on the CNTs super surface of claim 2, wherein the detection concentration range of the THz wave sensor is 1-80 ppm.
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| CN112362615B (en) * | 2020-10-23 | 2022-12-06 | 西安理工大学 | CNTs super surface and micro-channel integrated THz sensor and manufacturing method |
| CN113155161B (en) * | 2021-03-12 | 2023-02-21 | 西安理工大学 | Flexible CNTs terahertz metamaterial sensor and manufacturing method thereof |
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| DE102008016294A1 (en) * | 2008-03-28 | 2009-10-01 | Dritte Patentportfolio Beteiligungsgesellschaft Mbh & Co.Kg | Manufacturing method for a surface sensor, system and use of a surface sensor |
| WO2012111001A2 (en) * | 2011-02-14 | 2012-08-23 | Ben-Gurion University Of The Negev Research & Development Authority | Optical sensor with enhanced sensitivity |
| CN103575407A (en) * | 2012-07-18 | 2014-02-12 | 北京大学 | Terahertz radiation detector |
| CN103489943B (en) * | 2013-10-16 | 2016-06-01 | 电子科技大学 | The Terahertz absorption layer of carbon nanotube and metamaterial composite structure and preparation method |
| WO2017188438A1 (en) * | 2016-04-28 | 2017-11-02 | 国立大学法人東京工業大学 | Terahertz wave detection device and array sensor |
| JP7148986B2 (en) * | 2017-05-09 | 2022-10-06 | 学校法人 中央大学 | Terahertz wave detection device and terahertz wave detection system |
| CN109066095B (en) * | 2018-07-23 | 2020-08-04 | 西安理工大学 | Manufacturing method of broadband tunable terahertz wave absorber |
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